Synthesis of cyclometallated platinum(ii) complexes

ABSTRACT

A single-step method of making tetradentate platinum or palladium complexes is disclosed. The method advantageously allows the formation of a platinum or palladium complex in a single step, even with sterically hindered ligands, without the use of highly reactive intermediates. The compounds made by the disclosed method are useful in OLED applications.

The claimed invention was made by, on behalf of, and/or in connection with one or more of the following parties to a joint university corporation research agreement: Regents of the University of Michigan, Princeton University, The University of Southern California, and the Universal Display Corporation. The agreement was in effect on and before the date the claimed invention was made, and the claimed invention was made as a result of activities undertaken within the scope of the agreement.

FIELD OF THE INVENTION

The present invention relates to methods of forming platinum (Pt) or palladium (Pd) metal complexes in a single step. The disclosed method can form Pt and Pd complexes of even sterically hindered tetradentate ligands.

BACKGROUND

Opto-electronic devices that make use of organic materials are becoming increasingly desirable for a number of reasons. Many of the materials used to make such devices are relatively inexpensive, so organic opto-electronic devices have the potential for cost advantages over inorganic devices. In addition, the inherent properties of organic materials, such as their flexibility, may make them well suited for particular applications such as fabrication on a flexible substrate. Examples of organic opto-electronic devices include organic light emitting devices (OLEDs), organic phototransistors, organic photovoltaic cells, and organic photodetectors. For OLEDs, the organic materials may have performance advantages over conventional materials. For example, the wavelength at which an organic emissive layer emits light may generally be readily tuned with appropriate dopants.

OLEDs make use of thin organic films that emit light when voltage is applied across the device. OLEDs are becoming an increasingly interesting technology for use in applications such as flat panel displays, illumination, and backlighting. Several OLED materials and configurations are described in U.S. Pat. Nos. 5,844,363, 6,303,238, and 5,707,745, which are incorporated herein by reference in their entirety.

One application for phosphorescent emissive molecules is a full color display. Industry standards for such a display call for pixels adapted to emit particular colors, referred to as “saturated” colors. In particular, these standards call for saturated red, green, and blue pixels. Color may be measured using CIE coordinates, which are well known to the art.

One example of a green emissive molecule is tris(2-phenylpyridine) iridium, denoted Ir(ppy)₃, which has the following structure:

In this, and later figures herein, we depict the dative bond from nitrogen to metal (here, Ir) as a straight line.

As used herein, the term “organic” includes polymeric materials as well as small molecule organic materials that may be used to fabricate organic opto-electronic devices. “Small molecule” refers to any organic material that is not a polymer, and “small molecules” may actually be quite large. Small molecules may include repeat units in some circumstances. For example, using a long chain alkyl group as a substituent does not remove a molecule from the “small molecule” class. Small molecules may also be incorporated into polymers, for example as a pendent group on a polymer backbone or as a part of the backbone. Small molecules may also serve as the core moiety of a dendrimer, which consists of a series of chemical shells built on the core moiety. The core moiety of a dendrimer may be a fluorescent or phosphorescent small molecule emitter. A dendrimer may be a “small molecule,” and it is believed that all dendrimers currently used in the field of OLEDs are small molecules.

As used herein, “top” means furthest away from the substrate, while “bottom” means closest to the substrate. Where a first layer is described as “disposed over” a second layer, the first layer is disposed further away from substrate. There may be other layers between the first and second layer, unless it is specified that the first layer is “in contact with” the second layer. For example, a cathode may be described as “disposed over” an anode, even though there are various organic layers in between.

As used herein, “solution processible” means capable of being dissolved, dispersed, or transported in and/or deposited from a liquid medium, either in solution or suspension form.

A ligand may be referred to as “photoactive” when it is believed that the ligand directly contributes to the photoactive properties of an emissive material. A ligand may be referred to as “ancillary” when it is believed that the ligand does not contribute to the photoactive properties of an emissive material, although an ancillary ligand may alter the properties of a photoactive ligand.

As used herein, and as would be generally understood by one skilled in the art, a first “Highest Occupied Molecular Orbital” (HOMO) or “Lowest Unoccupied Molecular Orbital” (LUMO) energy level is “greater than” or “higher than” a second HOMO or LUMO energy level if the first energy level is closer to the vacuum energy level. Since ionization potentials (IP) are measured as a negative energy relative to a vacuum level, a higher HOMO energy level corresponds to an IP having a smaller absolute value (an IP that is less negative). Similarly, a higher LUMO energy level corresponds to an electron affinity (EA) having a smaller absolute value (an EA that is less negative). On a conventional energy level diagram, with the vacuum level at the top, the LUMO energy level of a material is higher than the HOMO energy level of the same material. A “higher” HOMO or LUMO energy level appears closer to the top of such a diagram than a “lower” HOMO or LUMO energy level.

As used herein, and as would be generally understood by one skilled in the art, a first work function is “greater than” or “higher than” a second work function if the first work function has a higher absolute value. Because work functions are generally measured as negative numbers relative to vacuum level, this means that a “higher” work function is more negative. On a conventional energy level diagram, with the vacuum level at the top, a “higher” work function is illustrated as further away from the vacuum level in the downward direction. Thus, the definitions of HOMO and LUMO energy levels follow a different convention than work functions.

More details on OLEDs, and the definitions described above, can be found in U.S. Pat. No. 7,279,704, which is incorporated herein by reference in its entirety.

SUMMARY OF THE INVENTION

A method of preparing a metal complex comprising combining at least one ligand L with a metal precursor to form a mixture, wherein the ligand L is at least bidentate, is provided. The metal precursor is a Pt or Pd compound containing at least one bidentate ligand L′, and no halogen is directly connected to the Pt or Pd. The mixture is reacted for a sufficient time to form a reaction product, wherein the reaction product has at least two atoms from ligand L bonded to the Pt or Pd, and wherein ligand L has at least one anionic carbon donor bonded to Pt or Pd. The reaction product is then recovered from the mixture.

In one aspect, the ligand L has the formula:

Formula I. In the compound of Formula I, rings A, B, C, and D are each independently a 5- or 6-membered carbocyclic or heterocyclic ring and ring C and ring D are optional. L₁, L₂, L₃, and L₄ are independently selected from the group consisting of a single bond, BR, NR, PR, O, S, Se, C═O, S═O, SO₂, CRR′, SiRR′, and GeRR′; wherein m2, m3, and m4 are 0 or 1. Z₁, Z₂, Z₃, and Z₄ are CH or N. R₁, R₂, R₃, and R₄ may represent mono-, di-, tri-, or tetra-substitutions, or no substitution. R, R′, R₁, R₂, R₃, and R₄ are independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof. Two adjacent substituents of R, R′, R₁, R₂, R₃, and R₄ are optionally joined to form a fused ring.

In one aspect, the ligand L has the formula:

Formula II, wherein m2, m3, and m4 are 0.

In one aspect, the ligand L has the formula:

Formula III, wherein m2 is 1 and wherein m3 and m4 are 0.

In one aspect, the ligand L has the formula:

Formula IV, wherein m2, m3, and m4 are 1.

In one aspect, the ligand L has the formula:

Formula V, wherein m2 and m3 are 1 and m4 is 0.

In one aspect, rings A, B, C, and D are independently selected from the group consisting of benzene, pyridine, imidazole, and pyrazole. In another aspect, at least one of ring A, B, C, and D is benzene.

In one aspect, two of Z₁, Z₂, Z₃ and Z₄ are CH, and two of Z₁, Z₂, Z₃ and Z₄ are N. In one aspect, the metal precursor is Pt compound.

In one aspect, the ligand L has the formula selected from:

wherein R₅ and R₆ are independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.

In one aspect, ligand L′ has the formula:

Formula VI, wherein X₁ and X₂ are independently selected from the group consisting of N, O, S, and P. In one aspect, X₁ and X₂ are independently selected from the group consisting of O and S. In another aspect, X₁ and X₂ are O.

In one aspect, ligand L′ has the formula:

Formula VII, and wherein R_(x), R_(y), and R_(z) are each independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.

In one aspect, R_(x), R_(y), and R_(z) are independently selected from the group consisting of alkyl, hydrogen, deuterium, and combinations thereof. In another aspect, R_(z) is hydrogen or deuterium, and R_(x) and R_(y) are independently selected from the group consisting of methyl, CH(CH₃)₂, and CH₂CH(CH₃)₂. In one aspect, R_(x) and R_(y) are methyl. In one aspect, the reaction time is at least 30 hours.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows an organic light emitting device.

FIG. 2 shows an inverted organic light emitting device that does not have a separate electron transport layer.

FIG. 3 shows an exemplary tetradentate ligand capable of being ligated by the disclosed method.

DETAILED DESCRIPTION

Generally, an OLED comprises at least one organic layer disposed between and electrically connected to an anode and a cathode. When a current is applied, the anode injects holes and the cathode injects electrons into the organic layer(s). The injected holes and electrons each migrate toward the oppositely charged electrode. When an electron and hole localize on the same molecule, an “exciton,” which is a localized electron-hole pair having an excited energy state, is formed. Light is emitted when the exciton relaxes via a photoemissive mechanism. In some cases, the exciton may be localized on an excimer or an exciplex. Non-radiative mechanisms, such as thermal relaxation, may also occur, but are generally considered undesirable.

The initial OLEDs used emissive molecules that emitted light from their singlet states (“fluorescence”) as disclosed, for example, in U.S. Pat. No. 4,769,292, which is incorporated by reference in its entirety. Fluorescent emission generally occurs in a time frame of less than 10 nanoseconds.

More recently, OLEDs having emissive materials that emit light from triplet states (“phosphorescence”) have been demonstrated. Baldo et al., “Highly Efficient Phosphorescent Emission from Organic Electroluminescent Devices,” Nature, vol. 395, 151-154, 1998; (“Baldo-I”) and Baldo et al., “Very high-efficiency green organic light-emitting devices based on electrophosphorescence,” Appl. Phys. Lett., vol. 75, No. 3, 4-6 (1999) (“Baldo-II”), which are incorporated by reference in their entireties. Phosphorescence is described in more detail in U.S. Pat. No. 7,279,704 at cols. 5-6, which are incorporated by reference.

FIG. 1 shows an organic light emitting device 100. The figures are not necessarily drawn to scale. Device 100 may include a substrate 110, an anode 115, a hole injection layer 120, a hole transport layer 125, an electron blocking layer 130, an emissive layer 135, a hole blocking layer 140, an electron transport layer 145, an electron injection layer 150, a protective layer 155, and a cathode 160. Cathode 160 is a compound cathode having a first conductive layer 162 and a second conductive layer 164. Device 100 may be fabricated by depositing the layers described, in order. The properties and functions of these various layers, as well as example materials, are described in more detail in U.S. Pat. No. 7,279,704 at cols. 6-10, which are incorporated by reference.

More examples for each of these layers are available. For example, a flexible and transparent substrate-anode combination is disclosed in U.S. Pat. No. 5,844,363, which is incorporated by reference in its entirety. An example of a p-doped hole transport layer is m-MTDATA doped with F.sub.4-TCNQ at a molar ratio of 50:1, as disclosed in U.S. Patent Application Publication No. 2003/0230980, which is incorporated by reference in its entirety. Examples of emissive and host materials are disclosed in U.S. Pat. No. 6,303,238 to Thompson et al., which is incorporated by reference in its entirety. An example of an n-doped electron transport layer is BPhen doped with Li at a molar ratio of 1:1, as disclosed in U.S. Patent Application Publication No. 2003/0230980, which is incorporated by reference in its entirety. U.S. Pat. Nos. 5,703,436 and 5,707,745, which are incorporated by reference in their entireties, disclose examples of cathodes including compound cathodes having a thin layer of metal such as Mg:Ag with an overlying transparent, electrically-conductive, sputter-deposited ITO layer. The theory and use of blocking layers is described in more detail in U.S. Pat. No. 6,097,147 and U.S. Patent Application Publication No. 2003/0230980, which are incorporated by reference in their entireties. Examples of injection layers are provided in U.S. Patent Application Publication No. 2004/0174116, which is incorporated by reference in its entirety. A description of protective layers may be found in U.S. Patent Application Publication No. 2004/0174116, which is incorporated by reference in its entirety.

FIG. 2 shows an inverted OLED 200. The device includes a substrate 210, a cathode 215, an emissive layer 220, a hole transport layer 225, and an anode 230. Device 200 may be fabricated by depositing the layers described, in order. Because the most common OLED configuration has a cathode disposed over the anode, and device 200 has cathode 215 disposed under anode 230, device 200 may be referred to as an “inverted” OLED. Materials similar to those described with respect to device 100 may be used in the corresponding layers of device 200. FIG. 2 provides one example of how some layers may be omitted from the structure of device 100.

The simple layered structure illustrated in FIGS. 1 and 2 is provided by way of non-limiting example, and it is understood that embodiments of the invention may be used in connection with a wide variety of other structures. The specific materials and structures described are exemplary in nature, and other materials and structures may be used. Functional OLEDs may be achieved by combining the various layers described in different ways, or layers may be omitted entirely, based on design, performance, and cost factors. Other layers not specifically described may also be included. Materials other than those specifically described may be used. Although many of the examples provided herein describe various layers as comprising a single material, it is understood that combinations of materials, such as a mixture of host and dopant, or more generally a mixture, may be used. Also, the layers may have various sublayers. The names given to the various layers herein are not intended to be strictly limiting. For example, in device 200, hole transport layer 225 transports holes and injects holes into emissive layer 220, and may be described as a hole transport layer or a hole injection layer. In one embodiment, an OLED may be described as having an “organic layer” disposed between a cathode and an anode. This organic layer may comprise a single layer, or may further comprise multiple layers of different organic materials as described, for example, with respect to FIGS. 1 and 2.

Structures and materials not specifically described may also be used, such as OLEDs comprised of polymeric materials (PLEDs) such as disclosed in U.S. Pat. No. 5,247,190 to Friend et al., which is incorporated by reference in its entirety. By way of further example, OLEDs having a single organic layer may be used. OLEDs may be stacked, for example as described in U.S. Pat. No. 5,707,745 to Forrest et al, which is incorporated by reference in its entirety. The OLED structure may deviate from the simple layered structure illustrated in FIGS. 1 and 2. For example, the substrate may include an angled reflective surface to improve out-coupling, such as a mesa structure as described in U.S. Pat. No. 6,091,195 to Forrest et al., and/or a pit structure as described in U.S. Pat. No. 5,834,893 to Bulovic et al., which are incorporated by reference in their entireties.

Unless otherwise specified, any of the layers of the various embodiments may be deposited by any suitable method. For the organic layers, preferred methods include thermal evaporation, ink-jet, such as described in U.S. Pat. Nos. 6,013,982 and 6,087,196, which are incorporated by reference in their entireties, organic vapor phase deposition (OVPD), such as described in U.S. Pat. No. 6,337,102 to Forrest et al., which is incorporated by reference in its entirety, and deposition by organic vapor jet printing (OVJP), such as described in U.S. patent application Ser. No. 10/233,470, which is incorporated by reference in its entirety. Other suitable deposition methods include spin coating and other solution based processes. Solution based processes are preferably carried out in nitrogen or an inert atmosphere. For the other layers, preferred methods include thermal evaporation. Preferred patterning methods include deposition through a mask, cold welding such as described in U.S. Pat. Nos. 6,294,398 and 6,468,819, which are incorporated by reference in their entireties, and patterning associated with some of the deposition methods such as ink-jet and OVJD. Other methods may also be used. The materials to be deposited may be modified to make them compatible with a particular deposition method. For example, substituents such as alkyl and aryl groups, branched or unbranched, and preferably containing at least 3 carbons, may be used in small molecules to enhance their ability to undergo solution processing. Substituents having 20 carbons or more may be used, and 3-20 carbons is a preferred range. Materials with asymmetric structures may have better solution processibility than those having symmetric structures, because asymmetric materials may have a lower tendency to recrystallize. Dendrimer substituents may be used to enhance the ability of small molecules to undergo solution processing.

Devices fabricated in accordance with embodiments of the invention may be incorporated into a wide variety of consumer products, including flat panel displays, computer monitors, medical monitors, televisions, billboards, lights for interior or exterior illumination and/or signaling, heads up displays, fully transparent displays, flexible displays, laser printers, telephones, cell phones, personal digital assistants (PDAs), laptop computers, digital cameras, camcorders, viewfinders, micro-displays, vehicles, a large area wall, theater or stadium screen, or a sign. Various control mechanisms may be used to control devices fabricated in accordance with the present invention, including passive matrix and active matrix. Many of the devices are intended for use in a temperature range comfortable to humans, such as 18 degrees C. to 30 degrees C., and more preferably at room temperature (20-25 degrees C.).

The materials and structures described herein may have applications in devices other than OLEDs. For example, other optoelectronic devices such as organic solar cells and organic photodetectors may employ the materials and structures. More generally, organic devices, such as organic transistors, may employ the materials and structures.

The terms halo, halogen, alkyl, cycloalkyl, alkenyl, alkynyl, arylkyl, heterocyclic group, aryl, aromatic group, and heteroaryl are known to the art, and are defined in U.S. Pat. No. 7,279,704 at cols. 31-32, which are incorporated herein by reference.

A method of preparing a metal complex comprising combining at least one ligand L with a metal precursor to form a mixture, wherein the ligand L is at least bidentate, is provided. The metal precursor is a Pt or Pd compound containing at least one bidentate ligand L′, and no halogen is directly connected to the Pt or Pd. The mixture is reacted for a sufficient time to form a reaction product, wherein the reaction product has at least two atoms from ligand L bonded to the Pt or Pd, and wherein ligand L has at least one anionic carbon donor bonded to Pt or Pd. The reaction product is then recovered from the mixture.

Direct metallation of multi-dentate ligands is desirable because it allows for efficient synthesis of the desired metal complex in a single step and avoids the use of hazardous materials such as alkyl lithium reagents, e.g. butyl lithium. A halide functional group is also often required for halogen-metal exchange, which usually complicates the synthesis. It is known that bidentate biscyclometallated platinum complexes such as cis-Pt(ppy)₂ (2 in Scheme 1) could not be prepared by direct cyclometallation reactions because the direct metallation with KPtCl₄ produced only a chloride bridged dinuclear monocyclometallated complex (1 in Scheme 1). Instead, cis-Pt(ppy)₂ is prepared from the transmetallation of Pt(SEt)₂Cl₂ with the corresponding organolithium reagents. (Scheme 1). However, as discussed above, generation of the organolithium reagent in Scheme 1 requires treatment of the phenyl pyridine ligand with an alkyl lithium reagent.

In contrast, the reaction of the tetradenate ligands with K₂PtCl₄ in acetic acid gave the desired bis-cyclometallated platinum complexes (cf. Huo et al. Inorg. Chrem. 2010, 49, 5107). Without being bound by theory, this result may be attributed to the fact of the second C—Pt bond formation is an intramolecular process that is generally considered to be more favorable than an intermolecular reaction (Scheme 2).

However, in the case of more sterically demanding ligand systems, the method illustrated in Scheme 2 generally fails to facilitate the direct ligation between the ligand and the metal precursor. For example, the reaction of ligand 3 with K₂PtCl₄ in acetic acid fails to form complex 4 as illustrated in Scheme 3.

It has been unexpectedly discovered that a metal precursor containing at least one bindentate ligand and containing no halogens bonded directly to the metal can effect the direct ligation of even sterically crowded ligands. The method is also suitable for ligands that lack steric crowding. The method advantageously does not require the lithiation of aromatic C—H bonds in order to effect the ligation. Instead, the desired product is formed directly by combining the metal precursor and the ligand, where the metal precursor is as described above. The reaction products may be recovered using conventional laboratory techniques, including, and without limitation, filtration, chromatography, sublimation, etc.

The method is illustrated in Scheme 4. For example, by using Pt(acac)₂ as a metal precursor, more sterically demanding ligands can be complexed with platinum(II). In contrast, treating the same ligands with K₂PtCl₄ in acetic acid gave no desired product. The acac (acetylacetone) ligand is a bidentate ligand that binds to the metal precursor through the two oxygen atoms contained in the ligand, and without being bound by theory, it is believed that bidentate ligands such as acac are better leaving groups and able to stabilize intermediate complexes of Pt or Pd prior to the formation of the final product. Similar bidentate ligands, which have been commonly used in the Pd/Pt metal-ligand exchange reactions, are those having coordinating atoms of O, N, S, and P. (see, e.g., Williams et al. Top. Curr. Chem. 2007, 281, 205; Eisenberg and Gray, Inorg. Chem. 2011, 50, 9741; Hissler et al. Coord Chem. Rev. 2000, 208, 115; Cummings et al. J. Am. Chem. Soc. 1996, 118, 1949; Liang Coord. Chem. Rev. 2006, 250, 1152 and references included therein). Due to the thermal stability of the precursor and reaction intermediate, the reaction can be carried out at high temperature, i.e. more than 200° C., to drive the complexation to completion. Additionally, the elimination of halogens from the reagents in the formation of the complex prevents the unintended incorporation of halogen moieties into the reaction products, which have been shown to be deleterious in OLED devices (see, e.g., Fleissner, A. et al. Chem. Mater. 2009, 21, 4288 and Andersson, G.; et al. Synth. Met. 2000, 113, 245). Selected results are summarized in Table 1.

TABLE 1 Comparison of Formation of Tetradentate Metal Complexes with the Claimed Method (Method B) vs. Using K₂PtCl₄ as Metal Precursor (Method A) Product from Method A Product from Method B Ligand K₂PtCl₄ route Pt(acac)₂ route

No product detected

No product detected

No product detected

No product detected

For each of the ligands tested, the claimed method, which uses a metal precursor as described above, resulted in the formation of the desired tetradentate metal complex. In contrast, use of metal precursors containing halogen ligands bound directly to the metal, and which had no bidentate ligand L′, resulted in no detectable product.

In one embodiment, the ligand L has the formula:

Formula I. In the compound of Formula I, rings A, B, C, and D are each independently a 5- or 6-membered carbocyclic or heterocyclic ring and ring C and ring D are optional. L₁, L₂, L₃, and L₄ are independently selected from the group consisting of a single bond, BR, NR, PR, O, S, Se, C═O, S═O, SO₂, CRR′, SiRR′, and GeRR′; wherein m2, m3, and m4 are 0 or 1. Z₁, Z₂, Z₃, and Z are CH or N. R₁, R₂, R₃, and R₄ may represent mono-, di-, tri-, or tetra-substitutions, or no substitution. R, R′, R₁, R₂, R₃, and R₄ are independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof. Two adjacent substituents of R, R′, R₁, R₂, R₃, and R₄ are optionally joined to form a fused ring.

The dashed circles in ligand L above are meant to indicate that rings C and D are optional.

When the ligand L makes a complex with metal M, atoms Z₁, Z₂, Z₃, and Z₄, when present, are bonded directly to metal M. When any one of Z₁, Z₂, Z₃, and Z₄ is CH, the bond is directly between the carbon atom in the CH and the metal, i.e. the carbon is a carbanion.

In one embodiment, the ligand L has the formula:

Formula II, wherein m2, m3, and m4 are 0.

In one embodiment, the ligand L has the formula:

Formula II, wherein m2 is I and wherein m3 and m4 are 0.

In one embodiment, the ligand L has the formula:

Formula IV, wherein m2, m3, and m4 are 1.

In one embodiment, the ligand L has the formula:

Formula V, wherein m2 and m3 are I and m4 is 0.

In one embodiment, rings A, B, C, and D are independently selected from the group consisting of benzene, pyridine, imidazole, and pyrazole. In another embodiment, at least one of ring A, B, C, and D is benzene.

In one embodiment, two of Z₁, Z₂, Z₃ and Z₄ are CH, and two of Z₁, Z₂, Z₃ and Z₄ are N. In one embodiment, the metal precursor is Pt compound.

In one embodiment, the ligand L has the formula selected from:

wherein R₅ and R₆ are independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.

In one embodiment, ligand L′ has the formula:

Formula VI, wherein X₁ and X₂ are independently selected from the group consisting of N, O, S, and P. In one embodiment, X₁ and X₂ are independently selected from the group consisting of O and S. In another embodiment, X₁ and X₂ are O.

In one embodiment, ligand L′ has the formula:

Formula VII, and wherein R_(x), R_(y), and R_(z) are each independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.

In one embodiment, R_(x), R_(y), and R_(z) are independently selected from the group consisting of alkyl, hydrogen, deuterium, and combinations thereof. In another embodiment, R_(z) is hydrogen or deuterium, and R_(x) and R_(y) are independently selected from the group consisting of methyl, CH(CH₃)₂, and CH₂CH(CH₃)₂. In one embodiment, R_(x) and R_(y) are methyl. In one aspect, the reaction time is at least 30 hours.

Combination with Other Materials

The materials described herein as useful for a particular layer in an organic light emitting device may be used in combination with a wide variety of other materials present in the device. For example, emissive dopants disclosed herein may be used in conjunction with a wide variety of hosts, transport layers, blocking layers, injection layers, electrodes and other layers that may be present. The materials described or referred to below are non-limiting examples of materials that may be useful in combination with the compounds disclosed herein, and one of skill in the art can readily consult the literature to identify other materials that may be useful in combination.

HIL/HTL:

A hole injecting/transporting material to be used in the present invention is not particularly limited, and any compound may be used as long as the compound is typically used as a hole injecting/transporting material. Examples of the material include, but not limit to: a phthalocyanine or porphryin derivative; an aromatic amine derivative; an indolocarbazole derivative; a polymer containing fluorohydrocarbon; a polymer with conductivity dopants; a conducting polymer, such as PEDOT/PSS; a self-assembly monomer derived from compounds such as phosphonic acid and sliane derivatives; a metal oxide derivative, such as MoO_(x); a p-type semiconducting organic compound, such as 1,4,5,8,9,12-Hexaazatriphenylenehexacarbonitrile; a metal complex, and a cross-linkable compounds.

Examples of aromatic amine derivatives used in HIL or HTL include, but not limit to the following general structures:

Each of Ar₁ to Ar⁹ is selected from the group consisting aromatic hydrocarbon cyclic compounds such as benzene, biphenyl, triphenyl, triphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, azulene; group consisting aromatic heterocyclic compounds such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine; and group consisting 2 to 10 cyclic structural units which are groups of the same type or different types selected from the aromatic hydrocarbon cyclic group and the aromatic heterocyclic group and are bonded to each other directly or via at least one of oxygen atom, nitrogen atom, sulfur atom, silicon atom, phosphorus atom, boron atom, chain structural unit and the aliphatic cyclic group. Wherein each Ar is further substituted by a substituent selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.

In one aspect, Ar¹ to Ar⁹ is independently selected from the group consisting of:

k is an integer from 1 to 20; X¹ to X⁸ is C (including CH) or N; Ar¹ has the same group defined above.

Examples of metal complexes used in HIL or HTL include, but not limit to the following general formula:

M is a metal, having an atomic weight greater than 40; (Y¹-Y²) is a bidentate ligand, Y¹ and Y² are independently selected from C, N, O, P, and S; L is an ancillary ligand; m is an integer value from 1 to the maximum number of ligands that may be attached to the metal; and m+n is the maximum number of ligands that may be attached to the metal.

In one aspect, (Y¹-Y²) is a 2-phenylpyridine derivative.

In another aspect, (Y¹-Y²) is a carbene ligand.

In another aspect, M is selected from Ir, Pt, Os, and Zn.

In a further aspect, the metal complex has a smallest oxidation potential in solution vs. Fc*/Fc couple less than about 0.6 V.

Host:

The light emitting layer of the organic EL device of the present invention preferably contains at least a metal complex as light emitting material, and may contain a host material using the metal complex as a dopant material. Examples of the host material are not particularly limited, and any metal complexes or organic compounds may be used as long as the triplet energy of the host is larger than that of the dopant. While the Table below categorizes host materials as preferred for devices that emit various colors, any host material may be used with any dopant so long as the triplet criteria is satisfied.

Examples of metal complexes used as host are preferred to have the following general formula:

M is a metal; (Y³-Y⁴) is a bidentate ligand, Y³ and Y⁴ are independently selected from C, N, O, P, and S; L is an ancillary ligand; m is an integer value from 1 to the maximum number of ligands that may be attached to the metal; and m+n is the maximum number of ligands that may be attached to the metal.

In one aspect, the metal complexes are:

(O—N) is a bidentate ligand, having metal coordinated to atoms O and N.

In another aspect, M is selected from Ir and Pt.

In a further aspect, (Y³-Y⁴) is a carbene ligand.

Examples of organic compounds used as host are selected from the group consisting aromatic hydrocarbon cyclic compounds such as benzene, biphenyl, triphenyl, triphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, azulene; group consisting aromatic heterocyclic compounds such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine; and group consisting 2 to 10 cyclic structural units which are groups of the same type or different types selected from the aromatic hydrocarbon cyclic group and the aromatic heterocyclic group and are bonded to each other directly or via at least one of oxygen atom, nitrogen atom, sulfur atom, silicon atom, phosphorus atom, boron atom, chain structural unit and the aliphatic cyclic group. Wherein each group is further substituted by a substituent selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.

In one aspect, host compound contains at least one of the following groups in the molecule:

R¹ to R⁷ is independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof, when it is aryl or heteroaryl, it has the similar definition as Ar's mentioned above.

k is an integer from 0 to 20.

X¹ to X⁸ is selected from C (including CH) or N.

Z¹ and Z² is selected from NR¹, O, or S.

HBL:

A hole blocking layer (HBL) may be used to reduce the number of holes and/or excitons that leave the emissive layer. The presence of such a blocking layer in a device may result in substantially higher efficiencies as compared to a similar device lacking a blocking layer. Also, a blocking layer may be used to confine emission to a desired region of an OLED.

In one aspect, compound used in HBL contains the same molecule or the same functional groups used as host described above.

In another aspect, compound used in HBL contains at least one of the following groups in the molecule:

k is an integer from 0 to 20; L is an ancillary ligand, m is an integer from 1 to 3.

ETL:

Electron transport layer (ETL) may include a material capable of transporting electrons. Electron transport layer may be intrinsic (undoped), or doped. Doping may be used to enhance conductivity. Examples of the ETL material are not particularly limited, and any metal complexes or organic compounds may be used as long as they are typically used to transport electrons.

In one aspect, compound used in ETL contains at least one of the following groups in the molecule:

R¹ is selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof, when it is aryl or heteroaryl, it has the similar definition as Ar's mentioned above.

Ar¹ to Ar³ has the similar definition as Ar's mentioned above.

k is an integer from 0 to 20.

X¹ to X⁸ is selected from C (including CH) or N.

In another aspect, the metal complexes used in ETL contains, but not limit to the following general formula:

(O—N) or (N—N) is a bidentate ligand, having metal coordinated to atoms O, N or N, N; L is an ancillary ligand; m is an integer value from 1 to the maximum number of ligands that may be attached to the metal.

In any above-mentioned compounds used in each layer of the OLED device, the hydrogen atoms can be partially or fully deuterated.

In addition to and/or in combination with the materials disclosed herein, many hole injection materials, hole transporting materials, host materials, dopant materials, exiton/hole blocking layer materials, electron transporting and electron injecting materials may be used in an OLED. Non-limiting examples of the materials that may be used in an OLED in combination with materials disclosed herein are listed in Table 2 below. Table 2 lists non-limiting classes of materials, non-limiting examples of compounds for each class, and references that disclose the materials.

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EXPERIMENTAL

General Method A:

A mixture of the ligand (1 mmol), K₂PtCl₄ (0.42 g, 1 mmol) and glacial acetic acid (60 mL) was degassed and refluxed under nitrogen for 45 h. After cooling to room temperature, the yellow to orange precipitates were collected by filtration, washed with water and methanol and dried in air. The crude materials were purified by chromatography on silica gel.

General Method B:

To a 50 mL Schlenk tube were added ligand (2 mmol), Pt(acac)₂ (2 mmol) and tridecane (10 drops). The mixture was degassed with nitrogen and heated in a sand bath (outside sand bath temperature was 230-240° C.) with stirring under a nitrogen atmosphere for the appropriate time. After cooling, the reaction mixture was dissolved with CH₂Cl₂ and subjected to flash column chromatography (SiO₂; 1:1 CH₂Cl₂:hexanes, v/v). The solid after column chromatography was re-crystallized from mixture of CH₂Cl₂ and methanol. The product was confirmed by ESI-MS.

Table 3 summarizes the synthetic results of using Method B to form Compounds 1-4. Compounds 1-4 could not be obtained using Method A.

TABLE 3 Summary of Synthetic Results Reaction Time Yield Compound (hours) % 1 36 100 2 16 6 3 16 5 4 16 6

It is understood that the various embodiments described herein are by way of example only, and are not intended to limit the scope of the invention. For example, many of the materials and structures described herein may be substituted with other materials and structures without deviating from the spirit of the invention. The present invention as claimed may therefore include variations from the particular examples and preferred embodiments described herein, as will be apparent to one of skill in the art. It is understood that various theories as to why the invention works are not intended to be limiting. 

1. A method of preparing a metal complex comprising: (a) combining at least one ligand L with a metal precursor to form a mixture; wherein the ligand L is at least bidentate; wherein the metal precursor is a Pt or Pd compound containing at least one bidentate ligand L′; wherein no halogen is directly connected to the Pt or Pd; (b) reacting the mixture for a sufficient time to form a reaction product; wherein the reaction product has at least two atoms from ligand L bonded to the Pt or Pd, wherein ligand L has at least one anionic carbon donor bonded to Pt or Pd; (c) recovering the reaction product from the mixture.
 2. The method of claim 1, wherein ligand L has the formula:

wherein rings A, B, C, and D are each independently a 5- or 6-membered carbocyclic or heterocyclic ring; wherein ring C and ring D are optional; wherein L₁, L₂, L₃, and L₄ are independently selected from the group consisting of a single bond, BR, NR, PR, O, S, Se, C═O, S═O, SO₂, CRR′, SiRR′, and GeRR′; wherein m2, m3, and m4 are 0 or 1; wherein Z₁, Z₂, Z₃, and Z₄ are CH or N; wherein R₁, R₂, R₃, and R₄ may represent mono-, di-, tri-, or tetra-substitutions, or no substitution; wherein R, R′, R₁, R₂, R₃, and R₄ are independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; wherein two adjacent substituents of R, R′, R₁, R₂, R₃, and R₄ are optionally joined to form a fused ring.
 3. The method of claim 2, wherein ligand L has the formula:

Formula II; wherein m2, m3, and m4 are
 0. 4. The method of claim 2, wherein the ligand L has the formula:

Formula III; wherein m2 is 1 and wherein m3 and m4 are
 0. 5. The method of claim 2, wherein the ligand L has the formula:

Formula IV; wherein m2, m3, and m4 are
 1. 6. The method of claim 2, wherein the ligand L has the formula:

Formula V; wherein m2 and m3 are 1 and m4 is
 0. 7. The method of claim 2, wherein rings A, B, C, and D are independently selected from the group consisting of benzene, pyridine, imidazole, and pyrazole.
 8. The method of claim 2, wherein at least one of ring A, B, C, and D is benzene.
 9. The method of claim 2, wherein two of Z₁, Z₂, Z₃ and Z₄ are CH, and two of Z₁, Z₂, Z₃ and Z₄ are N.
 10. The method of claim 1, wherein the metal precursor is Pt compound.
 11. The method of claim 2, wherein the ligand L has the formula selected from:

wherein R₅ and R₆ are independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.
 12. The method of claim 1, wherein ligand L′ has the formula:

Formula VI, wherein X₁ and X₂ are independently selected from the group consisting of N, O, S, and P.
 13. The method of claim 12, wherein X₁ and X₂ are independently selected from the group consisting of O and S.
 14. The method of claim 12, wherein X₁ and X₂ are O.
 15. The method of claim 14, wherein ligand L′ has the formula:

Formula VII, and wherein R_(x), R_(y), and R_(z) are each independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.
 16. The method of claim 15, wherein R_(x), R_(y), and R_(z) are independently selected from the group consisting of alkyl, hydrogen, deuterium, and combinations thereof.
 17. The method of claim 16, wherein R_(z) is hydrogen or deuterium, and R_(x) and R_(y) are independently selected from the group consisting of methyl, CH(CH₃)₂, and CH₂CH(CH₃)₂.
 18. The method of claim 17, wherein R_(x) and R_(y) are methyl.
 19. The method of claim 1, wherein the reaction time is at least 30 hours. 